CN102603466B - Preparation method of 1,1,2-trichloro-3-fluoropropene - Google Patents
Preparation method of 1,1,2-trichloro-3-fluoropropene Download PDFInfo
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- CN102603466B CN102603466B CN201210037410.4A CN201210037410A CN102603466B CN 102603466 B CN102603466 B CN 102603466B CN 201210037410 A CN201210037410 A CN 201210037410A CN 102603466 B CN102603466 B CN 102603466B
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Abstract
The invention provides a preparation method of 1,1,2-trichloro-3-fluoropropene. A nucleophilic substitution reaction between 1,1,2,3-tetrachloropropene and a nucleophilic fluorinating reagent is conducted to obtain 1,1,2-trichloro-3-fluoropropene with a molar ratio of 1:(1-5) and at a reaction temperature of 90-120 DEG C for 1-10h, wherein the nucleophilic fluorinating reagent is alkali metal fluoride, alkali metal hydrofluoride, tertiary amine hydrofluoride salt, fluorinated quaternary ammonium salt or fluorinated quaternary amine hydrofluoride salt. The preparation method provided by the invention is mainly used for preparing 1,1,2-trichloro-3-fluoropropene.
Description
Technical field
The present invention relates to a kind ofly 1,1, the preparation method of the chloro-3-fluorine of 2-tri-propylene, relates in particular to a kind ofly 1,1,2, and 3-tetrachloro propylene (TCP) and nucleophilic fluorination reagent generation nucleophilic substitution reaction obtain the preparation method of the chloro-3-fluorine of 1,1,2-tri-propylene.
Background technology
The latent value of ozone depletion of 2,3,3,3-tetrafluoeopropene (HFO-1234yf) is zero, and the latent value of Greenhouse effect is 4, and environmental performance is good, is considered to the ideal substitute of HFC-134a.The chloro-3-fluorine of 1,1,2-tri-propylene can be used as the reaction raw materials of preparation HFO-1234yf.
Patent WO2010045104 discloses 1, the preparation method of the chloro-3-fluorine of 1,2-tri-propylene, the method is that to take zellon and fluoromethane be reaction raw materials, at chlorine, tetracol phenixin, trichlorotoluene zotrichloride, hexachloroethane, under the radical initiators such as hexachloroacetone exist, 400～500 ℃ of reactions, generate the chloro-3-fluorine of 1,1,2-tri-propylene.But this patent does not provide concrete correlated response data, from disclosed content can find out that the method temperature of reaction is higher, transformation efficiency and selectivity lower.
Summary of the invention
Technical problem to be solved of the present invention is to overcome the deficiency existing in background technology, provides a kind of reaction conditions gentle, transformation efficiency and selectivity higher 1,1, the preparation method of the chloro-3-fluorine of 2-tri-propylene.
In order to solve the problems of the technologies described above, the present invention is with 1,1,2,3-tetrachloro propylene is raw material, can under gentle reaction conditions, there is nucleophilic substitution reaction with nucleophilic fluorination reagent, obtain 1,1, the chloro-3-fluorine of 2-tri-propylene, nucleophilic fluorination reagent and 1,1 wherein, 2, the mol ratio of 3-tetrachloro propylene is 1～5: 1, temperature of reaction is 90 ℃～120 ℃, and the reaction times is 1h～10h, and wherein nucleophilic fluorination reagent is that alkaline metal fluoride cpd, basic metal are fluoridized hydrogen salt, tertiary amine hydrofluoride, fluoridize quaternary amine or fluoridized quaternary amine hydrofluoride.
Alkaline metal fluoride cpd of the present invention is Sodium Fluoride, Potassium monofluoride or cesium fluoride; It is sodium bifluoride, potassium hydrogen fluoride, hydrogen fluoride caesium or bifluoride hydrogen potassium that basic metal is fluoridized hydrogen salt.
Tertiary amine hydrogen fluoride salts general formula of the present invention is: tertiary amine nHF, and 0 < n≤4.0 in formula, tertiary amine is that molecular formula is R
1r
2r
3the open chain amine of N, R in formula
1～R
3be C
1～C
10alkyl, or for containing-N=or-cyclammonium of N-group and 4～9 carbon atoms, comprise triethylamine, Tri-n-Propylamine, diisopropylethylamine, tri-n-butylamine, tri-n-amyl amine, dimethylcyclohexylamine, pyridine, 2-picoline, 2,4,6-trimethylpyridine, pyrimidine, pyrazine, N-methyl piperidine, N-methyl Pyrrolidine etc., but be not limited to above lifted compound.Preferred tertiary amine is triethylamine, Tri-n-Propylamine, diisopropylethylamine, tri-n-amyl amine, pyridine or 2-picoline.
N in tertiary amine hydrogen fluoride salts general formula tertiary amine nHF is very large to fluoridation activity influence.When n is bigger than normal, the nucleophilic fluorination ability of tertiary amine nHF is lower, and in certain scope, n is less, and the nucleophilic fluorination ability of tertiary amine nHF is just higher, and when n is less than normal, the alkalescence of tertiary amine nHF is bigger than normal, and reaction preference declines to some extent.The preferred n of the present invention is 1.0≤n≤3.0.
The quaternary amine of fluoridizing of the present invention is tetrabutyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, ethyl-trimethyl Neutral ammonium fluoride or benzyl tributyl Neutral ammonium fluoride; Quaternary amine hydrofluoride is tetrapropyl Neutral ammonium fluoride two hydrofluorides, tetrabutyl ammonium fluoride two hydrofluorides.
When nucleophilic fluorination reagent is that alkaline metal fluoride cpd or basic metal are while fluoridizing hydrogen salt, nucleophilic substitution reaction carries out under polyol solvent exists, wherein polyvalent alcohol is ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2,3-butanediol, glycol ether, Triethylene glycol, tetraethylene-glycol or glycerol.By controlling solvent adding amount, the amount concentration that makes 1,1,2,3-tetrachloro propylene is 1.0mol/L～15.0mol/L, preferably 1.0mol/L.
Compared with prior art, beneficial effect of the present invention: reaction conditions of the present invention is comparatively gentle, and its temperature of reaction is 90～120 ℃, and method temperature of reaction in documents is higher, its temperature of reaction is 400～500 ℃; The transformation efficiency of method of the present invention is higher good with selectivity, and its transformation efficiency can reach 98%, and selectivity can reach 90%; And method in documents does not provide concrete transformation efficiency and selective data.
Embodiment
Followingly the present invention is described in further detail to explanation in conjunction with the embodiments, but does not limit the scope of the invention.
In these embodiments, after reaction finishes, abstraction reaction liquid sample, gas chromatographic analysis reaction mass forms, thereby determines transformation efficiency and selectivity.
Embodiment 1
To magnetic agitation is housed, thermometer, in the dry there-necked flask of 50mL of condensing works, add 5.0g (0.028mol) 1, 1, 2, 3-tetrachloro propylene, 30mL glycol ether, open and stir, be heated to after 110 ℃, add again 8.1g (0.069mol) nucleophilic fluorination reagent Potassium monofluoride, react 1 hour, reaction solution is cooled to room temperature, filtering reacting liquid, underpressure distillation filtrate, under vacuum tightness 5kPa, collect the cut of 40～48 ℃, obtain 1, 1, the chloro-3-fluorine of 2-tri-propylene, 1, 1, 2, the transformation efficiency 96.4% of 3-tetrachloro propylene, 1, 1, the selectivity 92.2% of the chloro-3-fluorine of 2-tri-propylene.
Embodiment 2～4
Basic identical with the operation of embodiment 1, difference is that temperature of reaction is different with the reaction times, and reaction result is as shown in table 1.
Embodiment 5～9
Basic identical with the operation of embodiment 1, difference is that the solvent of embodiment 5～9 is ethylene glycol, reaction times 4h, and the mol ratio of nucleophilic reagent and 1,1,2,3-tetrachloro propylene is respectively 1: 1, and 1.5: 1,2: 1,2.5: 1,5: 1, reaction result was as shown in table 2.
Table 1
| Embodiment | Temperature of reaction/℃ | Reaction times/h | Transformation efficiency/% | Selectivity/% |
| 1 | 110 | 1.5 | 96.4 | 92.2 |
| 2 | 120 | 1.0 | 98.7 | 90.0 |
| 3 | 100 | 4 | 98.9 | 93.1 |
| 4 | 90 | 10 | 70.1 | 94.5 |
Table 2
| Embodiment | Nucleophilic fluorination reagent: TCP/ (mol:mol) | Transformation efficiency/% | Selectivity/% |
| 5 | 1.0 | 65.3 | 92.1 |
| 6 | 1.5 | 85.7 | 92.4 |
| 7 | 2.0 | 95.4 | 92.2 |
| 8 | 2.5 | 98.2 | 91.8 |
| 9 | 5.0 | 99.2 | 92.5 |
Embodiment 10～14
Basic identical with the operation of embodiment 1, difference is that the nucleophilic fluorination reagent adopting is different, and the mol ratio of nucleophilic fluorination reagent and TCP is 2.5, and reaction result is as shown in table 3.
Table 3
| Embodiment | Nucleophilic fluorination reagent | Transformation efficiency/% | Selectivity/% |
| 10 | NaF | 78.5 | 82.4 |
| 11 | CsF | 99.4 | 89.7 |
| 12 | KF·HF | 85 | 95 |
| 13 | CsF·HF | 90 | 94 |
| 14 | KF·2HF | 45 | 98 |
Embodiment 14～19
Basic identical with the operation of embodiment 1, difference is that solvent is different with the reaction times, and reaction result is as shown in table 4.
Embodiment 20
In the dry there-necked flask of the 50mL that magnetic agitation, thermometer, condensing works are housed, add successively nucleophilic fluorination reagent triethylamine 2HF (10.8g, 0.084mol), add subsequently 1,1,2,3-tetrachloro propylene (5.0g, 0.028mol), nucleophilic fluorination reagent and 1,1,2, the mol ratio of 3-tetrachloro propylene is 3, reacts 1 at 110 ℃ 2 hours, 1,2,3-tetrachloro propylene conversion is 90%, the chloro-3-fluorine of 1,1,2-tri-Propylene Selectivity is 95%.
Table 4
| Embodiment | Reaction solvent | Reaction times (h) | Transformation efficiency (%) | Selectivity (%) |
| 14 | Triethylene glycol | 3 | 98.7 | 92.1 |
| 15 | Tetraethylene-glycol | 2 | 99.2 | 93.7 |
| 16 | 1,2-PD | 4 | 87.3 | 80.2 |
| 17 | 1,3-PD | 4 | 86.9 | 80.8 |
| 18 | 2,3-butanediol | 5 | 95.4 | 76.5 |
| 19 | Glycerol | 1.5 | 99.4 | 89.6 |
Embodiment 21～33
Basic identical with the operation of embodiment 20, difference is that nucleophilic fluorination reagent used is different, and reaction result is as shown in table 5.
| Embodiment | Nucleophilic fluorination reagent | Transformation efficiency (%) | Selectivity (%) |
| 21 | Tri-n-Propylamine 2HF | 85 | 97 |
| 22 | Diisopropylethylamine 2HF | 80 | 98 |
| 23 | Dimethylcyclohexylamine 2HF | 95 | 96 |
| 24 | Tri-n-amyl amine 2HF | 80 | 96 |
| 25 | Pyridine 1HF | 78 | 95 |
| 26 | Pyrazine 1HF | 85 | 94 |
| 27 | 2-picoline 1HF | 78 | 92 |
| 28 | Methanaminium, N,N,N-trimethyl-, fluoride | 90 | 92 |
| 29 | Tetrapropyl Neutral ammonium fluoride | 94 | 93 |
| 30 | Ethyl-trimethyl Neutral ammonium fluoride | 85 | 90 |
| 31 | Benzyl tributyl Neutral ammonium fluoride | 94 | 92 |
| 32 | Tetrabutyl ammonium fluoride two hydrofluorides | 80 | 95 |
| 33 | Tetrapropyl Neutral ammonium fluoride two hydrofluorides | 75 | 95 |
Claims (2)
1. one kind 1, the preparation method of the chloro-3-fluorine of 2-tri-propylene, is characterized in that 1,1,2,3-tetrachloro propylene and nucleophilic fluorination reagent generation nucleophilic substitution reaction obtain 1, the chloro-3-fluorine of 1,2-tri-propylene, nucleophilic fluorination reagent and 1,1, the mol ratio of 2,3-tetrachloro propylene is 1～5:1, and temperature of reaction is 90 ℃～120 ℃, reaction times is 1h～10h, and wherein nucleophilic fluorination reagent is that alkaline metal fluoride cpd, basic metal are fluoridized hydrogen salt, tertiary amine hydrofluoride, fluoridize quaternary amine or fluoridized quaternary amine hydrofluoride; Described alkaline metal fluoride cpd is Sodium Fluoride, Potassium monofluoride or cesium fluoride; It is sodium bifluoride, potassium hydrogen fluoride or hydrogen fluoride caesium that described basic metal is fluoridized hydrogen salt; The general formula of described tertiary amine hydrogen fluoride salts is: tertiary amine nHF, and 0<n≤4.0 in formula, tertiary amine is triethylamine, Tri-n-Propylamine, diisopropylethylamine, tri-n-amyl amine, pyridine or 2-picoline; The described quaternary amine of fluoridizing is tetrabutyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, ethyl-trimethyl Neutral ammonium fluoride or benzyl tributyl Neutral ammonium fluoride; Described quaternary amine hydrofluoride is tetrapropyl Neutral ammonium fluoride two hydrofluorides, tetrabutyl ammonium fluoride two hydrofluorides.
2. according to claim 11,1, the preparation method of the chloro-3-fluorine of 2-tri-propylene, it is characterized in that nucleophilic substitution reaction carries out under polyol solvent exists, wherein polyvalent alcohol is ethylene glycol, 1,2-propylene glycol, 1,3-PD, 2,3-butanediol, glycol ether, Triethylene glycol, tetraethylene-glycol or glycerol.
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| WO2011044536A1 (en) * | 2009-10-09 | 2011-04-14 | Dow Global Technologies, Inc | Process for the production of chlorinated and/or fluorinated propenes and higher alkenes |
| CN102177117A (en) * | 2008-10-13 | 2011-09-07 | 陶氏环球技术有限责任公司 | Process for the production of chlorinated and/or fluorinated propenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102177117A (en) * | 2008-10-13 | 2011-09-07 | 陶氏环球技术有限责任公司 | Process for the production of chlorinated and/or fluorinated propenes |
| WO2011044536A1 (en) * | 2009-10-09 | 2011-04-14 | Dow Global Technologies, Inc | Process for the production of chlorinated and/or fluorinated propenes and higher alkenes |
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Effective date of registration: 20160519 Address after: 255300 Zhoucun City, Shandong province constant access road, No. 979, Patentee after: Shandong Huaan Modern Environmental Protection Technology Co., Ltd. Address before: 710065 Shaanxi province Xi'an Yanta District Zhang eight road No. 168 Patentee before: Xi'an Inst. of Modern Chemistry |